Certain diazolylaliphatic esters of thiophosphoric and dithiophosphoric acids

ABSTRACT

NEW ORGANIC PHOSPHORUS COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND USE IN PEST CONTROL ARE DISCLOSED. THE COMPOUNDS ARE THIA- OR OXADIAZOLONYL-DITHIOPHOSPHATES OF THE FORMULA   R2-O-P(=X)(-R1)-S-CH-N(-R3)&lt;(-N=C(-R4)-Y-C(=Y)-)   WHEREIN R1 REPRESENTS LOWER ALKYL, LOWER ALKOXY OR PHENYL, R2 IS LOWER ALKYL, R3 IS LOWER ALKYL, LOWER HALOGENOALKYL, LOWER ALKOXYALKYL, LOWER ALKYLTHIOALKYL OR PHENY, R4 IS HYDROGEN, LOWER ALKYL, LOWER ALKOXY, LOWER ALKYLTHIO, ALKOXY-ALKYL, ALKYLTHIOALKYL OR PHENYL AND X, Y AND Z EACH IS OXYGEN OR SULPHUR.

United States Patent 3,766,200 CERTAIN DIAZOLYLALIPHATIC ESTERS 0F THIO-PHOSPHORIC AND DITHIOPHOSPHORIC ACIDS Kurt Riifenacht, Basel,Switzerland, assignor to Ciba- Geigy Corporation, Ardsley, N.Y. NoDrawing. Filed June 29, 1971, Ser. No. 158,081 Int. Cl. C07d 91/62 US.Cl. 260-302 E 37 Claims ABSTRACT OF THE DISCLOSURE New organicphosphorus compounds, process for their production and use in pestcontrol are disclosed. The compounds are thiaoroxadiazolonyl-dithiophosphates of the formula wherein R represents loweralkyl, lower alkoxy or phenyl, R is lower alkyl, R,- is lower alkyl,lower halogenoalkyl, lower alkoxyalkyl, lower alkylthioalkyl or phenyl,R is hydrogen, lower alkyl, lower alkoxy, lower alkylthio, alkoxy-alkyl,alkylthioalkyl or phenyl and X, Y and Z each is oxygen or sulphur.

The present invention relates to new organic phosphorus compounds, toprocesses for the production thereof, and to the use of these compoundsfor the control of pests on animals and on plants.

The new organic phosphorus compounds correspond to the Formula I:

the symbols in this formula have the following meanings:

R represents lower alkyl, lower alkoxy or phenyl,

R represents lower alkyl,

R represents lower alkyl, lower halogenoalkyl, lower alkoxyalkyl, loweralkylthioalkyl, phenyl,

R represents hydrogen, lower alkyl, lower alkoxy, lower alkylthio,alkoxyalkyl, alkylthioalkyl, phenyl,

' and the symbols X, Y and Z represents, independently of wherein R andR each represent methyl or ethyl; R represents methyl, ethyl, C3H'7,chloromethyl, bromomethyl, -CH2OCH3, CH2SCH3, -CH2SC2H5,

or phenyl; R represents hydrogen, methyl, methoxy, ethoxy, iso-propoxy,methylthio or phenyl; and X, Y and Z each represent oxygen or sulphur.

The new organic phosphorus compounds of Formula I are produced accordingto the present invention by the simultaneous condensation of aphosphorus compound of the formula:

as such or in the form of one of its salts, with an aldehyde of theformula:

R -CHO (III) or with a reactive derivative of such an aldehyde, and witha diazole derivative of the formula:

the simultaneous condensation being performed in the aqueous solution ofstrong mineral acids having no oxidising action under the reactionconditions. In Formulae II to IV, R to R.,, X, Y and Z have the meaningsgiven under Formula I.

By simultaneous condensation is meant in the present case that thealdehyde component of Formula III is, on the one hand, simultaneouslybrought into contact with the phosphorus compound of Formula II and, onthe other hand, with the diazole component of Formula IV. This isachieved by the aldehyde component preferably being added to the mixtureof aqueous mineral acid, phosphorus compound and diazole. It is howeveralso possible to add the mixture of phosphorus compound and diazole tothe mixture of aldehyde component and aqueous mineral acid. Thisprocedure enables undesirable secondary reactions to be avoided, such asthe linkage of an aldehyde molecule either with two phosphorus radicalsor with two diazole radicals. The reaction temperatures are in the rangeof 15 to 60, preferably 20 to 45.

As strong mineral acids having no oxidising action under the reactionconditions are preferred for the process according to the invention thefollowing acids: sulphuric acid, hydrochloric acid, hydrobromic acid, aswell as mixtures of such acids. In the form of their aqueous solutionsthey serve as solvent and as condensation agent. For the condensationreaction are preferably used: 6098%, preferably -90%, sulphuric acid,2045%, preferably 2540%, hydrochloric acid, and 40-65%, preferably45-55% hydrobromic acid. The concentration of the mineral acid isdecisive for the occurrence of the condensation reaction, and hence forthe attainment of the optimum yield. In contrast to the concentration,the volume of mineral acid used is not critical. The mineral acid must,however, always be used in such a volume that the mechanical miscibilityof the reaction mixture is ensured. With the use of salts of thephosphorus compounds of Formula II or aldehyde derivatives, which, bythe consumption of acid or by dilution, displace the acid concentration,the volume of aqueous mineral acid must be so chosen that the acidconcentration does not fall below the above stated limits.

With regard to the phosphorus compounds of Formula II serving asstarting materials for the process according to the invention, these arethiophosphoric acids or thiophosphonic acids. These are used in thereaction in the free form, or in the form of their salts, preferably inthe form of their alkali metal salts or ammonium salts. The acids areliberated from the salts by the mineral acid. Usable as thiophosphoricacids and thiophosphonic acids of Formula II for the process accordingto the invention are, for example, the following:

0,0-dimethyl-thiophosphoric acid, 0,0-dimethyl-dithiophosphoric acid,0,0-diethyl-thiophosphoric acid, 0,0-diethyl-dithiophosphoric acid,O-methyl-O-ethyl-thiophosphoric acid, O-methyl-O-ethyl-dithiophosphoricacid,

'O-methyl-O-isopropyl-dithiophosphoric acid,

0,0-di-isopropyl-dithiophosphoric acid, O-methyl-dithio-methylphosphonicacid, O-ethyl-dithio-methylphosphonic acid,O-methyl-dithio-ethylphosphonic acid, O-ethyl-dithio-ethylphosphonicacid, O-methyl-dithio-phenylphosphonic acid,O-ethy1-dithio-phenylphosphonic acid.

For the process according to the invention, the aldehydes can be used inthe free form, in the form of their acetals, or in the form of oligomersand polymers. As acetals are preferred the dimethylacetals, the acetals,oligomers and polymers are cleaved by the strong aqueous mineral acid toproduce the free aldehydes. It is moreover possible to use aqueoussolutions of aldehydes, provided that by suitable measures, e.g. by theintroduction of hydrochloric acid gas, the hereby occurring dilution ofthe reaction medium is compensated for, and hence a decrease of themineral acid concentration avoided.

As aldehydes of Formula III, the following are, for example, usable forthe process according to the invention:

acetaldehyde, chloroacetaldehyde, dichloroacetaldehyde,trichloroacetaldehyde, bromoacetaldehyde, methoxyacetaldehyde,ethoxyacetaldehyde, propoxyacetaldehyde, isopropoxyacetaldehyde,methylthioacetaldehyde, ethylthioacetaldehyde, propylthioacetaldehyde,isopropylthioacetaldehyde, propionaldehyde, 3-chloropropionaldehyde,3-methoxypropionaldehyde, 3-cthoxypropionaldehyde,3-methylthiopropionaldehyde, butyraldehyde, 3-methoxybutyraldehyde,isobutyraldehyde, benzaldehyde.

Applicable as diazole derivatives of Formula IV are1,3,4-oxadiazol-(4H)-ones or 1,3,4-oxadiazole-5(4H)- thiones, and1,3,4-thiadiazol-5(4H)-ones or 1,3,4-thiadiazole-5(4H)-thiones; thefollowing are preferred:

1,3,4-oxadiazol-5 (4H) -one, Z-methyl-1,3,4-oxadiazol-5 (4H -one,2-ethyl-1,3,4-oxadiazol-5 (4H) -one,

2-propy1- 1,3,4-oxadiazol-5 (4H -one, 2-isopropyl-1,3,4-oxadiazol-5(4H)-one, Z-methoxymethyl-l ,3,4-oxadiazol-5 (4H) -one,Z-methyl-thiomethyl-1,3,4-oxadiazol-5 (4H) -one,2-phenyl-1,3,4-oxadiazol-5 (4H) -one, 2-methyl-1,3,4-oxadiazol-5 (4H)-thione, 2-ethyll ,3,4-oxadiazole-5 4H -thione,2-propyl-1,3,4-oxadiazole-5 (4H) -thione, 2-isopropy1-1,3,4-oxadiazole-54H) -thione, 2-phenyl-1,3 ,4-oxadiazole-S (4H) -thione, Z-methoxy- 1,3,4-thiadiazol-5 4H -one, 2-ethoxy-1,3,4-thiadiazol-5(4H)-one,2-propoxy-1,3,4-thiadiazol-5(4H)-one,

The new organic phosphorus compounds of Formula Ia:

R X Z wherein R represents the chloromethyl radical or the methylradical are obtained also by a modified process whereby a diazolecompound of Formula V:

wherein A represents a l-halogenoethyl radical or a 1-halogen-Z-chloroethyl radical is reacted with a phosphorus compound ofFormula II in the presence of an acidbinding agent, or with a salt ofsuch a phosphorus compound. The symbols R R R X, Y and Z in Formulae Iaand V have the meanings given under Formula I.

In the reaction of a diazole derivative of Formula V with a phosphoruscompound of Formula II, the halogen atom in l-position is exchanged.Either an acid-binding agent is therefore used or salts are used,especially the alkali metal and ammonium salts of phosphorus compoundsof Formula II. As acid-binding agents are preferred the alkali metalhydroxides and alkali metal carbonates; it is also possible, however, touse nitrogen bases, such as tertiary amines. The phosphorus compounds ofFormula II react with the diazole derivatives of Formula V withoutfurther difficulties at temperatures of between 0 and preferably at 10to 70 C. It is advisable to perform the reaction in the presence of asolvent or diluent inert to the reactants. Applicable in the first placeare lower aliphatic ketones such as acetone, methyl ethyl ketone,alkanols such as methanol, ethanol, isopropanol, esters such as ethylacetate, nitriles, N-alkylated acid amides, aromatic hydrocarbons suchas benzene, toluene, and water, as well as mixtures of such solventswith water.

The starting materials of Formula V have not been known hitherto. Theyare obtained by reaction of a diazole of Formula VI:

I CR| HN--N (VI) with acetaldehyde or chloroacetaldehyde and asubsequent, preferably however a simultaneous, treatment with ahalogenation agent such as thionyl chloride, phosphorus trichloride,phosphorus tribromide, phosphorus oxychloride, phosphorus pentachloride,R and Y in Formula VI have the meanings given under Formula I.

These reactions are performed in a solvent or diluent inert to thereactants. Most suitable for the preferred method of carrying out theinvention are halogenated hydrocarbons such as chloroform, halogenatedethanes, carbon tetrachloride. It is also possible to use, however,aromatic hydrocarbons such as benzene, chlorobenzene, etc. Where theprocedure is performed in stages, the 1st stage can be carried out inorganic solvents and in aqueous solution; for the halogenation stage(2nd stage) are then used the above stated halogenated hydrocarbons. Thereaction temperatures are in the range of 0-100 0., preferably from 20to 70 C.

Applicable as diazole derivatives of Formula V are1,3,4-oxadiazol-(5(4H)-ones or 1,3,4-oxadiazole-5(4H)- thiones and1,3,4-thiadiazol-5(4H)-ones or 1,3,4-thiadiazole-5(4H)-thiones, e.g. thefollowing:

4-( 1'-chloroethyl l ,3,4-oxadiazol-5 4H) -one,

4-(1-bromoethyl(1,3,4-oxadiazol-5(4H)-one,

4-( 1',2-dichloroethyl -1,3,4-oxadiazol-5 4H) -one,

4-( 1-bromo-2'-chloroethyl)1,3,4-oxadiazol-5 (4H) -one,

4- 1'-chloroethyl) -2-methyl-1,3,4-oxadiazol-5 (4H )-one,

4- 1'-bromoethyl) -2-methyl-1,3,4-oxadiazol-5 (4H -one,

4-( 1,2-dichloroethyl)-2-methyl-1,3,4-oxadiazol-5 (4H) one,

4- 1'-bromo-2'-chloroethyl)-2-methyl-1,3,4-oxadiazol- 5 (4H) -one,

4- 1-chloroethyl) -2-methoxy-1,3,4-thiadiazol-5 (4H) one,

4- 1-bromoethyl) -2-methoxy-1,3,4-thiadiazol-5 4H one,

4-(l',2'-dichloroethyl)-2-methoxy-1,3,4-thiadiazol- 5 4H -one,

4-( 1-bromo-2'-chloroethyl) -2-methoxy-1,3,4-thiadiazol- 5 (4H) -one,

4-( 1-chloroethyl)-2-cthoxy-1,3,4-thiadiazol-5 4H one,

4-( l-bromoethy1)-2-ethoxy-1,3,4-thiadiazol-5 4H) -one,

4-( 1',2'-dichloroethyl)-2-ethoxy-1,3,4-thiadiazol-5 (4H one,

4-( 1'-bromo-2'-chloroethyl) -2-ethoxy-1,3,4-thiadiazol- 5 (4H -one,

4- l'-chloroethyl)-2-isopropxy-1,3,4-thiadiazol-5 (4H) one,

4- 1'-bromoethy1)-2-isopropoxy-1,3 ,4-thiadiazol-5 (4H one,

4-( 1',2'-dichloroethyl)-2-isopropxy-1,3,4-thiadiazol- 5 4H -one,

4-(1'-bromo-2'-chloroethyl)-2-isopropxy-1,3,4-thiadiazol- The compoundsof Formula I are suitable for the control of the most diverse animal andvegetable pests. The said compounds are particularly suitable for thecontrol of insects and types belonging to the order acarina. Theseactive substances have a good to very good action as contact and stomachpoisons, combined with a systemic action against insects and theirdevelopment stages, such as, e.g. against insects of the familiesCurcolionidae, Bruchididae, Dermistidae, Tenebrionidae andChrysomelidae, e.g. grain weevils (Sitophilus granarius), common beanweevils (Bruchidius obtectus), larder beetles (Dermestes vulpinus),yellow mealworms (Tenebri molitor), Colorado potato beetles(Leptinotarsa decemlineata); against insects of the family Pyralididae,e.g. Mediterranean flour moths (Ephestia kiihniella); against insects ofthe family Blattidae, e.g. cockroaches (Phyllodromiw germanical,Periplaneta americana, Blatta riental is); against insects of the familyAphididae, e.g. bean Pseudococcidae, e.g. citrus mealybugs (Planococcuscitri), and of the family Locustidae, e.g. migratory locusts (L0- custamigratoria). Tests on the said bean aphids, citrus 6 mealybugs andmigratory locusts showed an excellent systemic action.

Furthermore the new organic phosphorus compounds of Formula I aresuitable for the control of ectoand endoparasitic insects occurring inanimals, and of types of the order acarina and their development stages,such as insects of the family Muscidae, e.g. Musca domestica (housefly), Stomoxys calcitrans (stable fly); insects of the familyCalliphoridae, e.g. Calliphora erythrocephala (blue blowfly), Lucilimcuprina (gold-fly), Callitroga Tabanus bovinus (gadfly); insects of thefamily Culicidae, e.g. Anopheles spp., Culex spp., Aedes spp.(mosquitoes); Arachnids of the family Argasidae, e.g. Ornithodorusmoubata (soft tick), Argas reflexus (pigeon tick); Arachnids of thefamily Ixodidae, e.g. Ixodes ricinus (castor bean tick), of the familyDermacentor reticulatus, Rhz'picephalus bursa and Boo philus microplus(ticks); Arachnids of the family Dermanyssidae, e.g. Dermanyssusgallz'nae, Bdellonyssus bacon, of the family Demodicidae, e.g. Demodexcanis, of the family Trombiculidae, e.g. T rombicula autumnalis; of thefamily Acaridae, e.g. Acarus farinae and siro; of the familyGlycyphagidae, e.g. Glycyphagus domesticus; of the family Sarcoptidae,e.g. Sarcoptes spp. (mange mite) and of the family Psoroptidae, e.g.Psoroptes spp. (Mange mite).

In admixtures with synergists and similarly acting auxiliaries, such asdibutyl succinate, piperonyl butoxide, olive oil, peanut oil, etc., therange of action of the active substances according to the invention isbroadened and, in particular, the insecticidal and acaricidal actionimproved. Likewise, the insecticidal action can be appreciably extendedand adapted to suit existing circumstances by the addition of otherinsecticides, such as, e.g. phosphoric, phosphonic, thioanddithiophosphoric acid esters and amides, halogenated hydrocarbons andanalogs of DDT-active substances, as well as pyrethrines and synergiststhereof, acaricidal active substances such as halogenobenzilic acidesters, insecticidal and acaricidal carbamates, e.g. oximecarbamat-es,arylcarbamates and carbamates of enolisable heterocycles.

In the concentrations used for the control of endoparasites, the activesubstances are not toxic, and are tolerated very well by domestic anduseful animals.

The active substances of Formula I can be used on their own or togetherwith suitable carriers and/or other additives. Suitable carriers andadditives can be solid or liquid, and they correspond to the substancescommon in formulation practice. 7

Agents according to the invention are produced in a manner known per seby the intimate mixing and grinding of active substances of the generalFormula I with suitable carriers, optionally with the addition ofdispersing agents or solvents which are inert to the active substances.The active substances can be obtained and used in the following forms:

solid preparations:

dusts, scattering agents, granulates, (coated granulates, impregnatedgranulates and homogeneous granulates) liquid preparations:

(a) water-dispersible concentrates of the active substance: wettablepowders, pastes, emulsions; (b) solutions.

The solid preparations (dusts, scattering agents, granulates) areproduced by the mixing of the active substances with solid carriers.Suitable carriers are, e.g. kaolin, talcum, bole, loess, chalk,limestone, ground limestone, Attaclay, dolomite, diatomaceous earth,precipitated silicic acid, alkaline-earth silicates, sodium andpotassium aluminum silicates (feldspar and mica), calcium and magnesiumsulphates, magnesium oxide, ground synthetic materials, fertilisers suchas ammonium sulphate, ammonium. phosphates, ammonium nitrate, urea,ground vegetable products such as bran, bark dust, sawdust, groundnutshells, cellulose powder, residues of plant extractions, activecharcoal, etc., alone or in admixture with each other.

The particle size of the carriers is for dusts advantageously up toabout 0.1 mm.; for scattering agents from about 0.075 mm. to 0.2 mm.;and for granulates 0.2 mm. or coarser.

The concentrations of active substance in the solid preparation formsare from 0.5 to 80%.

To these mixtures may also be added additives stabilising the activesubstance, and/or non-ionic, anion-active, and cation-active substances,which, for example, improve the adhesiveness of the active substances onplants and on parts of plants (adhesives and agglutinants), and/orensure a better wettability (wetting agents) and dispersibility(dispersing agents). Suitable adhesives are, for example, the following:olein/lime mixture, cellulose derivatives (methyl cellulose,carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl anddialkyl phenols having to ethylene oxide radicals per molecule and 8 to9 carbon atoms in the alkyl radical, ligninsulphonic acids, their alkalimetal and alkaline-earth metal salts, polyethylene glycol ethers(carbowaxes), fatty alcohol polyethylene glycol ethers having 5 toethylene oxide radicals per molecule and 8 to 18 carbon atoms in thefatty alcohol moiety, condensation products of ethylene oxide, propyleneoxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation productsof urea and formaldehyde, as well as latex products.

Water-dispersible concentrates of active substance, i.e. wettablepowders pastes and emulsion concentrates, are agents which can bediluted with water to obtain any desired concentration. They consist ofactive substance, carrier, optionally additives which stabilise theactive substance, surface-active substances, and antifoam agents and,optionally, solvents. The concentration of active substance in theseagents is 5 to 80%.

The wettable powders and the pastes are obtained by the mixing andgrinding of the active substances with dispersing agents and pulverulentcarriers, in suitable devices, until homogeneity is attained. Suitablecarriers are, e.g. those previously mentioned in the case of solidpreparations. It is advantageous in some cases to use mixtures ofdifferent carriers. As dispersing agents it is possible to use, e.g.:condensation products of sulphonated naphthalene and sulphonatednaphthalene derivatives with formaldehyde, condensation products ofnaphthalene or of naphthalenesulphonic acids with phenol andformaldehyde, as well as alkali, ammonium and alkaline-earth metal saltsof ligninsulphonic acid, also alkylaryl sulphonates, alkali salts andalkaline-earth metal salts of dibutyl naphthalenesulphonic acid, fattyalcohol sulphates such as salts of sulphated hexadecanols,heptadecanols,-

octadecanols, and salts of sulphated fatty alcohol glycol ether, thesodium salt of oleyl methyl tauride, ditertiary acetylene glycols,dialkyl dilauryl ammonium chloride, and fatty acid alkali-metal andalkaline-earth metal salts.

Suitable anti-foam agents are, for example, silicones.

The active substances are so mixed, ground, sieved and strained with theabove mentioned additives that the solid constitutent in the case ofwettable powders has a particle size not exceeding 0.02 to 0.04 mm. andin the case of pastes not exceeding 0.03 mm. For the preparation ofemulsion concentrates and pastes are used dispersing agents such asthose mentioned in the preceeding paragraphs, organic solvents, andwater. Suitable solvents are, e.g. the following: alcohols, benzene,xylenes, toluene, dimethylsulphoxide, and mineral oil fractions boilingin the range of 120 to 350. The solvents must be practically odourless,non-phytotoxic, inert to the active substances, and not readilyinflammable.

Furthermore, the agents according to the invention can be used in theform of solutions. For this purpose, the active substance (or severalactive substances) is (or are) dissolved in suitable organic solvents,mixtures of 8 solvents, or water. As organic solvents it is possible touse aliphatic and aromatic hydrocarbons, their chlorinated derivatives,alkylnaphthalenes, mineral oils on their own or in admixture with eachother. The solutions should contain the active substances in aconcentration of from 1 to 20%.

To broaden their sphere of action, it is also possible to add to thedescribed agents according to the invention, in addition to theinsecticides and acaricides, e.g. fungicides, bactericides,fungistatics, bacteriostatics or nematocides. The agents according tothe invention may also contain fertilisers, trace elements, etc.

The content of active substance in the above described agents is between0.1 and it is to be mentioned that in the case of application from anaeroplane, or by means of other suitable application devices,concentrations of up to 99.5% are used, or even pure active substance isapplied.

In the following are described preparations of the new active substancesof the general Formula I. The term parts denotes parts by weight.

DUST

The following substances are used for the production of(a) a 5%, and(b)a 2% dust:

5 parts of the active substance of Formula I, e.g. 0,0-dimethyl-S-[2-methoxy-1,3,4-thiadiazol 5(4H) onyl- (4 -isobutyryl 1')]-dithiophosphate,

95 parts of talcum;

2 parts of the active substance of Formula I, e.g. 0,0- diethyl-S-[Zmethoxy 1,3,4 thiadiazol 5(4H)- onyl (4) -isobutyryl( 1) ]-dithiophosphate,

1 part of highly dispersed silicic acid,

97 parts of talcum.

The active substances are mixed and ground with the carriers.

GRANULATE The following substances are used for the preparation of a 5%granulate:

5 parts of 0,0-dimethyl-S-[ 1,34-oxadiazol-5 (4H )-onyl- 4) -ethyl( 1)]-dithiophosphate,

0.5 parts of epoxidised vegetable oil,

2 parts of light silicic acid 50,

92.5 parts of ground limestone 0.4-0.8 mm.

The active substance is mixed with the epoxidised vegetable oil and themixture dissolved with 6 parts of acetone. The thus obtained solution issprayed on to crushed limestone, and the acetone then evaporated invacuo. The light silicic acid is thereupon added.

WE'ITABLE POWDER The following constituents are used for the preparationof (a) a 40%, (b) a 50%, (c) a 25%, and (d) a 10% wettable powder:

40 parts of 0,0-diethyl-S-[Z-methoxy-1,3,4-thiadiazol- 5 (4H) -onyl( 4)-2'-chloroethyl-( 1') J-dithiophosphate, 5 parts of sodium ligninsulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts ofsilicic acid;

25 parts of 0,0-diethyl-S-[2-ethoxy-1,3,4-thiadiaz0l-5- (4H) -onyl (4)-2-chloroethyl-( 1') ]-dithiophosphate, 5 parts of sodium salt ofligninsulphonic acids, sulphite liquor powder, sodium salt, 1 part ofalkylaryl sulphonate (Tinovetin B"), 20 parts of Champagne chalk, 20parts of sodium aluminium silicate, 29 parts of kaolin;

10 parts of 0,0-diethyl-S-[2-isopropoxy-1,3,4-thiadiazol- 5(44)-onyl(4)-2-chloroethyl-( 1) J-dithiophosphate,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture then being ground in suitable mills and rollers.Wettable powders are obtained which can be diluted with water to obtainsuspensions of any desired concentration.

EMULSIFIABLE CONCENTRATE The following constituents are mixed togetherto produce a 25% emulsifiable concentrate:

25 parts of 0,0-diethyl-S-[1,3,4-oxadiazol-5 (4H)-onyl- (4) -ethyl( 1'-diethiophosphate,

2.5 parts of epoxidised vegetable oil,

10 parts of a mixture of nonylphenolpolyoxyethylene andcalcium-dodecylbenzene-sulphonate,

62.5 parts of xylene.

This concentrate can be diluted with Water to obtain emulsions of anydesired concentration.

EXAMPLE 1 To a mixture of 64 g. of pure concentrated sulphuric acid and16 g. of ice are successively added, at room temperature, 40 g. ofpotassium salt of 0,0-dimethyldithiophosphoric acid and 26 g. ofZ-methoxy-1,3,4-thiadiazol- 5(4H)-one. An amount of 12 g. ofacetaldehyde is then slowly added dropwise at 30 whilst thoroughstirring is maintained; the mixture is afterwards stirred for a further3 hours at 30. The mixture is then cooled to and 200 ml. of water areadded dropwise with cooling. The precipitated oil is taken up in ether,the ether solution washed with sodium bicarbonate solution and withwater, dried, and the ether distilled off. By molecular distillation at140/ 0.05 torr are obtained '54 g. of 0,0-dimethyl-S-[-methoxy1,3,4-thiadiazol-(4H)-onyl(4)-ethyl(1')]-dithiophosphate as pale yellowoil.

Calculated (percent): C, 26.57; H, 4.14; N, 8.86; P, 9.81; S, 30.41.Found: (percent) C, 26.51; H, 4.14; N, 9.09; P, 9.43; S, 30.11.

EXAMPLE 2 The same compound as in Example 1 is obtained also in thefollowing manner:

(a) To a mixture of 26 g. of 2-methoxy-1,3,4-thiadiazol-5(4H)-one, 150ml. of chloroform and 36 g. of thionyl chloride are added dropwise 20 g.of acetaldehyde, the temperature being thereby maintained between 20 and30. After several hours stirring is obtained a pale yellow solution. Thesolution is heated to boiling and re fluxed for one hour. After afractionated distillation are obtained 30 g. of2-methoxy-4-(1'-chloroethyl)-1,3,4-thiadiazol-5(4H)-one as pale yellowoil, B.P. 83-85 /0.5 torr.

(b) 35 g. of potassium salt of 0,0-dimethyldithiophosphoric acid and 30g. of 2-methoxy-4-(1-chloroethyl)- 1,3,4-thiadiazol-5(4H)-one aredissolved in 150 ml. of acetone. Stirring is carried out for 4 hours at40, and the acetone is distilled off in vacuo. Water is added to the 10residue, the precipitated oil is taken up in ether, the ether solutionwashed with sodium hydrogen carbonate solution and with water. Afterdrying and distilling off the ether, molecular distillation is preformedin high vacuum. An amount of 15 g. of 0,0-dimethyl-S-[2-methoxy-1,3,4-thiadiazol 5(4H) onyl(4) ethyl(1')]-dithiophosphate passes over at 0.07torr.

EXAMPLE 3 To a mixture of 68 g. of pure concentrated sulphuric acid and12 g. of ice are successively added, at room temperature, 46 g. ofpotassium salt of 0,0-diethyldithiophosphoric acid and 26 g. of2-methoxy-1,3,4-thiadiazol- 5(4H)-one. An amount of 11 g. of paraldehydeis then slowly added dropwise, and the mixture is stirred for a further3 hours at 35. The mixture is cooled to 0 and, with cooling, 200 ml. ofwater are added dropwise. The product precipitates immediately incrystalline form. After recrystallisation from 70 ml. of methanol areobtained 36 g. of 0,0 diethyl S 2-methoxy-1,3,4-thiadiazol-5(4H)-onyl(4)-ethyl(1) ]-dithiophosphate in the form of colourlesscrystals, M.P. 53-55 Calculated (percent): C, 31.38; H, 4.98; N, 8.13;P, 9.01; S, 27.92. Found (percent): C, 31.41; H, 4.89; N, 8.18; P, 9.14;S, 27.99.

EXAMPLE 4 If the acetaldehyde in Example 1 is replaced by 15 g. ofpropionaldehyde, the procedure being otherwise the same, an oil isobtained, after the ether has been distilled off, which is caused tocrystallise by trituration. After recrystallisation from 65 ml. ofmethanol are obtained 43 g. of0,0-dimethyl-S-[Z-methoxy-l,3,4-thiadiazol-5(4H)-onyl(4)-propyl(1')]-dithiophosphate in the form of colourless crystals,M.P. 38-40.

Calculated (percent): C, 29.08; H, 4.58; N, 8.48; P, 9.40; S, 29.12.Found (percent):-C, 29.46; H, 4.66; N, 8.88; P, 9.12; S, 28.94.

EXAMPLE 5 To a mixture of 60 g. of pure concentrated sulphuric acid and20 g. of ice are successively added, at room temperature, 48 g. ofpotassium salt of 0,0-diethyldithiophosphoric acid and 26 g. of2-methoxy-1,3,4-thiadiazol- 5(4H)-one. An amount of 17 g. ofisobutyraldehyde is added dropwise at 30-35, with vigorous stirring, inthe course of half an hour; stirring is then continued for a further 3hours at 30. The mixture is afterwards cooled to 0 and, with cooling,200 ml. of water are added dropwise, The product crystallises outimmediately. By recrystallisation from 350 ml. of methanol are obtained61 g. of 0,0-diethyl-S-[Z-methoxy-1,3,4-thiadiazol-5(4H)- only(4)isobutyl(l)]-dithiophosphate, M.P. 104-105.

Calculated (percent): C, 35,47; H, 5.69; N, 7.52; P, 8.33; S, 25.83.Found (percent): C, 35.42; H, 5.63; N, 7.46; P, 8.34; S, 25.69.

EXAMPLE 6 If the acetaldehyde in Example 1 is replaced by 22 g. ofbenzaldehyde, then is obtained using otherwise the same procedure, withthe dropwise addition of Water to the reaction mixture, an immediatelycrystallising product (see also Example 3). The product is filtered offand carefully dried. After recrystallisation from chloroform/ petroleumether are obtained 62 g. of 0,0-dimethyl-S- [2-methoxy-1,3,4 thiadiazol5 (4H) onyl(4) benzyl]- dithiophosphate in the form of colourlesscrystals, M.P. 5658.

Calculated (percent): C, 38.08; H, 4.00; N, 7.40; P, 8.20; S, 25.42.Found (percent): C, 37.80; H, 4.05; N, 7.31; P, 8.21; S, 25.71.

EXAMPLE 7 To a mixture of 64 g. of pure concentrated sulphuric acid and16 g. of ice are successively added, at room temperature, 37 g. ofammonium salt of 0,0-dimethyldithiophosphoric acid and 20 g. of2-methyl-1,3,4-oxadiazol-5(4H)-one. An amount of 11 g. of metaldehyde isslowly added at 35 with vigorous stirring, and the mixture stirred for afurther 3 hours at 35 The mixture is then cooled to and to it are addeddropwise, with cooling, 200 ml. of water. The product therebycrystallises out. After recrystallisation from 80 ml. of methanol areobtained 32 g. of0,0-dimethyl-S-[2-methyl-l,3,4-oxadiaZol-5-(4H)-onyl(4)-ethyl-(1)-dithiophosphatein the form of colourless crystals, M.P. 65 66.

Calculated (percent): C, 29.57; H, 4.61; N, 9.85; P, 10.92; S, 22.55.Found (percent): C, 29.79; H, 4.43; N, 9.73; P. 10.87; S, 22.78.

EXAMPLE 8 To a mixture of 70 g. of pure concentrated sulphuric acid and10 g. of ice are alternately added 42 g. of potassium salt of0,0-dimethyldithiophosphoric acid and 17 g. of1,3,4-oxadiazol-5(4H)-one. An amount of 13 g. of propionaldehyde is thenslowly added dropwise at 40, whilst vigorous stirring is maintained;stirring is afterwards continued for a further 3 hours at 40. Themixture is then cooled to 0, and 200 ml. of water are added dropwise.The precipitated oil is taken up in ether, the ether solution washedwith sodium bicarbonate solution and with water, dried, and the etherdistilled off. The oil remaining behind gradually crystallises. Byrecrystallisation from 40 ml. of methanol are obtained 22 g. of 0,0-dimethyl-S-[1,3,4-oxadiazol-5 (4H)-onyl(4) propyl(1')]- dithiophosphatein the form of colourless crystals, M.P. 51-53.

Calculated (percent): C, 29.57; H, 4.51; N, 9.85; P, 10.92; S, 22.55:Found (percent): C, 29.70; H, 4.60; N, 9.90; P, 10.90; S, 22.50.

EXAMPLE 9 In a mixture of 128 g. of pure concentrated sulphuric acid and32 g. of ice are reacted at 30, in the manner described in Example 1, 92g. of potassium salt of 0,0- diethyldithiophosphoric acid and 40 g. of2-methyl-1,3,4- oxadiazol-5(4H)-one with 32 g. of isobutyraldehyde. Theoil isolated by extraction with ether is subjected at 125/ 0.02 torr tomolecular distillation. The oil thereupon commences to crystallise.After recrystallisation from 100 ml. of methanol, an amount of 60 g. of0,0-diethyl-S-[2- methyl-1,3 ,4-oxadiazol-5 (4H) -onyl (4 -isobutyl- 1)dithiophosphate is obtained in the form of colourless oil, M.P. 42-43.

Calculated (percent): C, 38.81; H, 6.22; N, 8.23; P, 9.12; S, 18.84.Found (percent): C, 38.70; H, 6.30; N, 8.20; P, 9.30; S, 18.80.

EXAMPLE 10 To 100 ml. of concentrated hydrochloric acid (ca. 37%) areadded 40 g. of potassium salt of 0,0-dimethyldithiophosphoric acid and26 g. of 2-methoxy-1,3,4-thiadiazol- 5(4H)-one. Hydrochloric acid gas issimultaneously fed in at 30, and 60 g. of a 30% aqueous solution ofchloroacetaldehyde are slowly added dropwise. The feeding in ofhydrochloric acid gas continues and stirring is maintained for a further3 hours at 30; the mixture is thereupon poured into 150 ml. of water.The precipitated oil is taken up in ether, the ether solution washedwith sodium bicarbonate solution and with water, dried, and the etherdistilled off. The oil remaining behind is caused to crystallise bytrituration. By recrystallisation from 60 ml. of methanol are obtained43 g. of 0,0-dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5(4H)-onyl(4) 2'chloroethyl (1')]-dithiophosphate in the form of colourless crystals,M.P. 39-40.

Calculated (percent): C, 23.97; H, 3.45; N, 7.99; P, 8.85; S, 27.42; Cl,10.11. Found (percent): C, 24.11; H, 3.53; N, 8.09; P, 8.76; S, 27.55;Cl, 10.44.

EXAMPLE 1 l A product identical to that in Example 10 can be obtainedalso in the following manner:

To a mixture of 77 g. of pure concentrated sulphuric acid and 11 g. ofice are added, at room temperature, 42 g. of potassium salt of0,0-dimethyldithiophosphoric acid and 26 g. ofZ-methoxy-1,3,4-thiadiazol-5(4H)-one. An amount of 25 g. ofchloroacetaldehyde-dimethylacetal is then added dropwise at 40, withvigorous stirring, in the course of half an hour. Stirring is continuedfor a further 3 hours at 40; the mixture is then cooled to 0, and 220ml. of water are added dropwise. The further preparation as described inExample 10 yields 52 g. of 0,0-dimethyl-S-[Z-methoxy-l,3,4-thiadiazol-5(4H) onyl (4)-2'-chloroethyl(1')]-dithiophosphate, M.P. 3940.

EXAMPLE 12 (a) An amount of 26 g. of 2-methoxy-1,3,4-thiadiazol- 5(4H)-one is suspended in g. of a 30% aqueous solution ofchloroacetaldehyde. The suspension is heated to 35 2 ml. of an aqueous10% sodium carbonate solution are added, and stirring is continued for24 hours at room temperature. Two liquid phases are formed. Extractionwith ether is carried out, the ether solution dried, and concentrated ina water-jet vacuum. The oily intermediate product is dissolved in 50 ml.of chloroform, and to the solution are quickly added at 5 60 g. ofthionyl chloride. Stirring is carried out for one hour at roomtemperature, and for a further hour with refluxing. Readily volatileconstituents are distilled off at 40 in a waterjet vacuum, and theresidue is subsequently distilled in high vacuum. Thus obtained are 31g. of 2-methoxy-4-(1', 2'-dichloroethyl)-l,2,4thiadiazol-5(4H)-one aspale yellow oil, B.P. 899l/0.03 torr.

(b) 26 g. of potassium salt of 0,0-diethyldithiophosphoric acid and 24g. of the 2-methoxy-4-(1,2'-dichloroethyl)-1,3,4-thiadiazol-5(4H)-oneproduced by the above described process are stirred in 100 ml. ofacetone for 4 hours at 35 The acetone is distilled 01f in vacuo and tothe oily residue are added 100 ml. of ice water; the residue is stirreduntil it solidifies in crystalline form. By recrystallisation frommethanol are obtained 20 g. of 0,0-diethyl-S-[2-methoxy-1,3,4-thiadiazol5 (4H)-onyl(4)-2'chloroethyl(l)]-dithiophosphate, M.P. 50-5l.

EXAMPLE 13 A compound identical to that given in Example 12 is obtainedif the potassium salt of 0,0-dimethyldithiosphosphoric acid in Example11 is replaced by 46 g. of the potassium salt of0,0-diethyldithiophosphoric acid. With otherwise the same procedure areobtained 49 g. of 0,0-diethyl-S-[2-methoxy-1,3,4-thiadiazol-5(4H)-onyl(4) 2'-chloroethyl(1')]-dithiophosphate.

EXAMPLE 14 To 100 ml. of pure concentrated hydrochloric acid (d.=1.19)are successively added, at room temperature, 42 g. of potassium salt of0,0-dimethyldithiophosphoric acid and 29 g. of2-ethoxy-1,3,4-thiadiazol-5(4H)-one. Hydrochloric acid gas is fed at 30into the mixture being vigorously stirred, and simultaneously are addeddropwise 60 g. of a 30% aqueous solution of chloroacetaldehyde. Stirringis maintained for a further 3 hours at 30 with the continued feeding inof hydrochloric acid gas. The mixture is then poured on to g. of ice andthe precipitated oil is taken up in ether; the ether solution is washeduntil free of acid, dried, and ether distilled off. The obtained oilcrystallises and is recrystallised from methanol. Thus obtained are 48g. of 0,0-dimethyl-S-[2-ethoxy- 1,3,4 thiadiazol5(4H)-onyl(4)-2'-chloroethyl(1)]- dithiophosphate, M.P. 5658.

Calculated (percent): C, 26.34; H, 3.88; N, 7.69; P, 8.51; S, 26.38; Cl,9.72. Found (percent): C, 26.56, H, 3.86; N, 7.78; P, 8.44; S, 26.66;Cl. 9.80.

1? EXAMPLE 15 To a mixture of 114 g. of pure concentrated sulphuric acidand 16 g. of ice are added, at room temperature, 32 g. of2-phenyl-1,3,4-oxadiazol-5(4H)-one and 42 g. of potassium salt of0,0-dimethyldithiophosphoric acid. An amount of 25 g. ofchloroacetaldehyde-dimethylacetal is then slowly added dropwise at 40whilst vigorous stirring is maintained; stirring is then continued for afurther 3 hours at 40. The mixture is thereupon cooled to and 250 ml. ofwater are added dropwise. The precipitated oil is processed by beingtaken up in ether in the usual manner. The residue is caused tocrystallise by trituration. After recrystallisation from ethylacetate/petroleum ether is obtained a product melting somewhatindefinitely at 68-73; the product consists mainly of 0,0-dimethyl-S- [2phenyl 1,3,4-oxadial-5(4H)-onyl(4)-2'-chloroethyl- (1')]-dithiophosphate.

Calculated (percent): C, 37.85; H, 3.70; N, 7.36; P, 8.16; S, 16.84; Cl,9.31. Found (percent): C, 38.60; H, 3.76; N, 7.81; P, 7.75; S, 16.30;Cl, 9.01.

EXAMPLE 16 To a mixture of 77 g. of pure concentrated sulphuric acid and11 g. of ice are added, at room temperature, 38 g. of ammonium salt of0,0-dimethyldithiophosphoric acid and 26 g. of2-methoxy-1,3,4-thiadiazol-5(4H)-one. An amount of 34 g. ofbromoacetaldehyde-dimethylacetal is then added dropwise at 40, withvigorous stirring, in the course of half an hour. Stirring is continuedfor a further three hours at 40; the reaction mixture is then cooled to0, and 220 ml. of water are added dropwise. The precipitated oil istaken up in ether, the ether solution Washed with sodium bicarbonatesolution and with water, dried, and the ether distilled off. The residueremaining is crystallised. After recrystallisation from 110 ml. ofmethanol are obtained 50 g. of 0,0-dimethyl-S- [2 methoxy1,3,4-thiadiazol-5(4H)-onyl(4)-2'-bromoethyl(1')]-dithiophosphate in theform of colourless crystals, M.P. 39-41.

Calculated (percent); C, 21.27; H, 3.06; N, 7.09; P, 7.86; S, 24.33; Br20.22. Found (percent): C, 31.62; H, 3.11; N, 7.06; P, 7.86; S, 24.18;Br, 20.58.

EXAMPLE 17 If in Example 16 the ammonium salt of0,0-dimethyldithiophosphoric acid is replaced by 48 g. of potassium saltof 0,0-diethyldithiophosphoric acid, then are obtained, with otherwisethe same procedure, 53 g. of 0,0- diethyl S[Z-methoxy-1,3,4-thiadiazol-5(4H)-onyl(4)-2'-bromoethyl(1')]dithiophosphate, M.P. 45 47.

Calculated (percent): C, 25.53; H, 3.81; N, 6.62; P, 7.33; S, 22.72; Br,18.88. Found (percent): C, 25.61; H, 3.75; N, 6.67; P, 7.23; S, 22.54;Br, 18.94.

EXAMPLE 18 To a mixture of 57 g. of pure concentrated sulphuric acid and8 g. of ice are added 29 g. of ammonium salt of0,0-dimethyldithiophosphoric acid and 19.5 g.2-methoxy-1,3,4-thiadiazol-5(4H)-one. An amount of 18 g. ofmethoxy-acetaldehyde-dimethylacetal is then added dropwise at 40, withvigorous stirring, in the course of half an hour, and stirring iscontinued for a further 3 hours at 40. The mixture is afterwards cooledto 0 and 160 m1. of water are added dropwise. The precipitated oil istaken up in ether, the ether solution washed with sodium bicarbonatesolution and with water, and dried. The residue remaining after theether has been distilled off crystallises. After recrystallisation from45 ml. of methanol are obtained 29 g. of 0,0-dimethyl-S-[2-methoxy 1,3,4thiadiazol-5(4H)-onyl(4)-2'-methoxyethyl- (1)]-dithiophosphate in theform of colourless crystals, M.P. 36-37.

Calculated (percent): C, 27.74; H, 4.37; N, 8.09; P, 8.96; S, 27.77.Found (percent): C, 27.52; H, 4.41; N, 8.04; P, 8.98; S, 27.51.

l 4 EXAMPLE 19 An amount of 28 g. ofmethylthioacetaldehydedimethylacetal is added dropwise at 30, withvigorous stirring and in the course of half an hour, to a mixture of 64g.

of pure concentrated sulphuric acid, 16 g. of ice, 42 g. of potassiumsalt of 0,0-dimethyldithiophosphoric acid and 30 g. of2-methylthio-1,3,4-thiadiazol-5(4H)-one. The reaction mixture is stirredfor a further 3 hours at 30; it is then cooled to 0 and 200 ml. of waterare added dropwise. The precipitated oil is purified by extraction withether and isolated, as in Example 18. It crystallises after the etherhas been distilled off. By recrystallisation from ml. of methanol, 55 g.of 0,0- dimethyl S [Z-methylthio 1,3,4 thiadiazol-5(4H)-onyl(4)-2'-methylthioethyl(1') ]-dithiophosphate are obtained in theform of colourless crystals, M.P. 48-49.

Calculated (percent): C, 25.38; H, 4.00; N, 7.40; P, 8.20; S, 42.36.Found (percent): C, 25.40; H, 4.09; N, 7.53; P, 8.08; S, 4209.

EXAMPLE 20 An amount of 30 g. of ethylthioacetaldehydedimethylacetal isadded dropwise at 30, with vigorous stirring and in the course of halfan hour, to a mixture of 64 g. of pure concentrated sulphuric acid, 16g. of ice, 42 g. of potassium salt of 0,0-dimethyldithio phosphoric acidand 32 g. of 2-isopropoxy-1,3,4-thiadiazol-5(4H)-one. The reactionmixture is stirred for a further 3 hours at 30, and the procedure thencarried out analogously to that described in Example 18. The oilremaining after the ether has been distilled off is subjected tomolecular distillation in high vacuum at /0.025 torr. Thus obtained are70 g. of 0,0-dimethyl-S-[2-isopropoxy-l,3,4- thiadiazol 5 (4H) onyl(4) 2ethylthioethyl(l)]- dithiophosphate as pale yellow oil.

Calculated (percent): C, 32.66; H, 5.23; N, 6.92; P, 7.67; S, 31.71.Found (percent): C, 32.59; H, 5.43; N, 6.92; P, 7.60; S, 31.43.

EXAMPLE 21 An amount of 33 g. of isopropylthioacetaldehydedimethylacetalis added dropwise, analogously to Example 20, to a mixture of 64 g. ofpure concentrated sulphuric acid, 16 g. of ice, 48 g. of potassium saltof 0,0-diethy1- dithiophosphoric acid and 29 g. of2-ethoxy-1,3,4-thiadiazol-5(4H)-one. Using the same procedure areobtained, by molecular distillation in high vacuum at 160/ 0.02 torr, 73g. of 0,0-diethyl-S-[2-ethoxy-1,3,4-thiadiazol 5 (4H) onyl(4) 2isopropylthioethyl(1')]- dithiophosphate as pale yellow oil.

Calculated (percent): C, 36.09; H, 5.82; N, 6.48; P, 7.17; S, 29.65.Found (percent): C, 36.29; H, 5.90; N, 6.55; P, 6.81; S, 29.34.

EXAMPLE 22 acid and 32 g. of Z-phenyl-l,3,4-oxadiazol-5(4H)-one. I

An amount of 28 g. of methylthioacetaldehyde-dimethylacetal is addeddropwise to the above mixture at 40 in the course of half an hour withvigorous stirring. Stirring is carried out for a further three hours at40; the reaction mixture is then cooled to 10 and, with cooling, areadded dropwise 250 ml. of water. The precipitated oil is isolated andpurified by extraction with ether analogously to Example 18. The residueremaining after the ether has been distilled off crystallises. Afterrecrystallisation from 70 ml. of methanol are obtained 44 g. of 0,0-dimethyl S [2-phenyl 1,3,4 oxadiazol-5(4H)-onyl-(4)-2'-methylthioethyl(1')]-dithiophosphate in the form of colourlesscrystals, M.P. 56-58.

Calculated (percent): C, 39.78; H, 4.37; N, 7.14; P, 7.91; S, 24.51.Found (percent): C, 39.76; H, 4.24; N, 7.25; P, 7.73; S, 24.29.

1 5 EXAMPLE 23 An amount of 11 g. of acetaldehyde is added dropwise at30, with vigorous stirring and in the course of half an hour, toamixture of 64 g. of pure concentrated sulphuric acid, 16 g. of ice, 38g. of ammonium salt of 0,0-dimethyldithiophosphoric acid and 30 g. of2-methoxy 1,3,4 thiadiazole-5(4H)-thione. Stirring is continued for afurther three hours at 30; the mixture is then cooled to and 200 ml. ofwater are added dropwise. The precipitated oil is isolated, analogouslyto Example 18, by extraction with ether. By molecular distillation at150/ 0.02 torr are obtained 43 g. of 0,0- dimethyl S[Z-methoxy-1,3,4-thiadiazole-(4H) -thion-4-yl-ethyl(1')]-dithiophosphate in the form of a pale yellow oil.

Calculated (percent): C, 25.29; H, 3.95; N, 8.43; P, 9.34; S, 38.58.Found (percent): C, 25.56; H, 3.97; N, 8.46; P, 9.16; S, 38.22.

EXAMPLE 24 An amount of g. of metaldehyde is slowly added at 40, withvigorous stirring, to a mixture of 114 g. of pure concentrated sulphuricacid, 16 g. of ice, 37 g. of ammonium salt of0,0-dimethyldithiophosphoric acid and 32 g. of2-phenyl-1,3,4-oxadiazol-5 (4H)-one. Stirring is continued for a further3 hours at 40. A crystalline product hereby precipitates. The mixture isthen cooled to 0; an amount of 250 ml. of water is carefully addeddropwise, the solid material is filtered off and crystallised from 150ml. of methanol. Thus obtained are 41 g. of 0,0-dimethyl S[2-phenyl-1,3,4-oxadiazol-5(4H)-on- 4-yl-ethyl-(1) ]-dithiophosphate,M.P. 75-77.

Calculated (percent): C, 41.60; H, 4.37; N, 8.09; P, 8.96; S, 18.52.Found (percent): C, 41.34; H, 4.45; N, 8.23; P, 9.12; S, 18.68.

The analogously produced 0,0-diethyl derivative melts at 62-64.

EXAMPLE 25 To a mixture of 80 g. of pure concentrated sulphuric acid and9 g. of ice are successively added, with slight cooling, 35 g. ofammonium salt of 0,0-dimethylmonothiophosphoric acid and 26 g. of2-methoxy-1,3,4-thiadiazol-5(4H)-one. An amount of 25 g. ofchloroacetaldehyde-dimethylacetal is then slowly added dropwise at 40with vigorous stirring; stirring is afterwards continued for a further 4hours at 40. The mixture is then cooled to 0 and to it are addeddropwise, with good cooling, 240 m1. of water; the precipitated greasyresidue is taken up in ether; a fine granular precipitate herebyobtained is then filtered off; the now clear ether solution washed withsodium bicarbonate solution and with water, dried, and the etherdistilled off. The dark brown oil remaining behind is firstly cleared at50/0.05 torr of volatile constituents, and then subjected at 140/0.005torr to molecular distillation. Thus obtained are g. of not quite pure0,0-dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5(4H)-on-4-y1-(2 chloroethyl)(1')] thiophosphate as a pale yellow oil. In the thin-layerchromatogram, a nonpolar impurity is visible as a secondary spot.

Calculated (percent): C, 25.12; H, 3.62; N, 8.37; P, 9.27; S, 19.15; Cl,10.59. Found (percent): C, 26.30; H, 3.8; N, 9.1; P, 8.6; S, 19.2; C1,11.00.

Analogously to Examples 1 to 25 are produced the following compounds:

TABLE-Continued Melting point] boiling Compounds point 0 ,0-diethyl-S-[2-methylthio-1,3,4-thladlazol-5(4H)-onyl(4)-ethyl(l)L-dithiophosphate 42-44 0,0-dimetyl-S-[1,3,4-oxadlazol-5(4H)-onyl(4)-ethyl(1')]- dithiophosphate. l0. 02O ,0 -diethyl-S-[1,3,4-oxadlazol-5 (4H) -ony1 (4) -ethyl (1'dithiophosph are 125% oz 0 ,0-diethy1-S-[?rmethyl-1,3,4-oxadiazo1-5(4H)-ony1(4) ethyl (1]-dithiophosphate 5051 O ,O-diethy1-S-[?rmethoxy-1,3,4-thiadiazo1-5(4H)-onyl(4)-propyl(1')]-dithiophosphate 4648 0 ,0-dlmethyl-S-[2-methyl-1,3,4-oxadlazo1-5 (411)-ony1 (4)-propy1(1)-di]thlophosphate 71-73 0 ,0-dlethyl-S-[2-methy1-1,8,4-oxadiazol-5 (4H) -onyl (4)-propyl(1)-dithlophosphate /0.02 0,0-dimeth I-S-[Z-phenyl-l,3,4oxadiazo1-5(4H)-ony1(4)- propyl(1) -dithiophosphate 58-60 O ,0-diethyl-S-[2-pheny11,3,4-oxadiazo1-5(4H)-ony1(4)-propyl(1)1-dithiophosphate O ,0-dimethyl-S-[2methoxy-1,3,4-thladlazol-6(4H) -onyl(4)- isobutyl(1)]-dithiophos hate fi6-58 O,O-dimethyl-S-[2methy -1,3,4-oxadiazol-5(4H)-onyl(4)- isobutyl(1)]-dithiophosphate 7981 0,0-diethyl-S-[2ethoxy-1,3,4-thiadlchloroethyl(1)-dlth1ophosphate I0. 01 0 ,0-dimethyLS-[iLisopropoxy-l,3,4-thiadlazo1-5 (4H) -ony1- (4)-2'-chloroethyl (1)]-d1thiophosphate 6486 0,0-d1ethy1-S[2'iospropoxy-1,3,4-thiadlazol-5 (4H) -onyl (4)-2-chl0r0ethyl(1')]-dithl0phosphate /0.01 0 ,0-dimethyl-S-[2methy1thio-1,3,4-thladiazol-5 (4H) -ony1-(4)-2-ehloroethyl(1)l-dithoiphosphate 45-46 0 ,0-diethy1-S-[2-methylthio-1 ,3,4-thiadlazo1-5(4H)-onyl(4)-2-ch10roethyl(1)]-dith1ophosphate 145l0. 01 O ,0 -diethyl-S-[2-phen.yl-1 ,3,4-oxadiazo1-5 (4H) -onyl(4) -2'chloroethyl(1')]-dithiophosphate O ,0-dlmethyl-S-[2-ethoxy-1,3,4-thladiazol-5(4H)-onyl(4)-2'-bromoethyl(1')]-dithiophosphate 7071.6 0 ,O'diethyI-S-[Z-ethoxy-1,3,4-thiadlazo1-5 (4H)-onyl (4) -2brom0ethy1(1)]-dithiophosphate 150l0.01 O ,0dimethy1-S-[2-methylthlo-1,3,4-t hladiazol-fi (4H) (4) -2-bromoeth-yl (1')]-dithlophosphate.150l0. 03 0 ,0 'diethyl-S-[Z-methylthlo-l,3,4-thladiaz2-bromoethy1(1)]41ithiophosphate 160l0.020,0-dimethyl-S-[2-methoxy-1,3,4-thladiaz01-5(4H)-onyl(4)-2-methylthioethyl(1')]-dithiophosphate 50-52 0 ,0 -diethy1-S-[-2methoxy-l ,3,4-thladiazol-5 (4H) -onyl (4) -2-methylthio-ethyl(1')]-dithiophosphate 2830 O,0-dimethy1-S-[2-ethoxy-1,3,4-thiadiazol-5 (4H) -onyl (4) -2-methylthio-ethyl(1' )-]dithi0phosphate [SP-520,0-diethyl-S-[2-ethoxy-1,3,4-thiadiazol-5(4H)-onyl(4)-2'-methy1thio-ethy1(1')]-dithiophosphate /0.040,0-dimethyl-S-[2-isopropoxy-1 3,4'thiadiazo1-5(4H)-onyl(4)-2-methy1thio-ethyl(1)] dlthiophosphate -690,0-diethyl-S-l2-isopropoxy-1,3,4-thiadiazol-5(4H) -onyl(4)- 155/0. 052-methylthioethyl(1')]-dithi0ph0sphato 155/0.05 0,0-diethyl-S-[Z-methylthio-l,3,4-thiadiazol-5 (4H)onyl(4)-2-methylthio-ethyl(1)]-dithiophosphate-. /0.0250,0diethy1-S-[2-phenyl-1,3,4-oxadiazol-5(4H)-onmethy1thio-ethyl(1)l-dlthiophosphate0,0-dimethy1-S-[2-methoxy-1,3,4-th1adiazol-5(4H)-onyl(4)-2-ethylthio-ethyl(1)l-dithiophosphate 160/0.040,0-diethyl-S-[2-meth0xy-1,3,4-thiadiazol-5(4H)-onyl(4)-2-ethylthio-ethyl(1')]-dithiophosphate 160/0.030,0-d.imethyl-S-[2-ethoxy-1,3,4'thiadiaz01-5(4H)-ony1(4)-2-ethylthio-ethyl(1)]-dithiophosphate 46470,0-diethyl-S-[2-ethoxy-1,3,4-thiadiazol-5(4H)-onyl(4)2-ethylthio-ethyl(1')]-dithioph0sphate. 160/0.01 0,0-diethyl-S-[2-isoprooxy-1,3,4'thiad1azo1-5(4H)-0n 1(4) 2-ethylthio-ethyl(1)-dithiophosphate160/0.03 0,0-dimethyl-S-[Z-methoxy-l,3,4-thiadiazo1-5(4H2-isopropylthio-ethyl(1)]-dithi0ph0sphate.. 150/0.020,0-diethy1-S-[2-meth0xy-1,3,4-thiadlazol-5(4H yl(4)-2-isopropy1thioethyl(1')]-dithiophosphate 150/0.020,0-dimethyl-S-[2ethoxy-1,3,4-thiad.iazol-5(4H)-0ny1(4)-2-isopropylthi0-ethy1(1')]-dithi0phosphate 160/0.010,0-dimethyl-S[2-isopropoxy-1,3,4t;hiadiazol-5(4H)-0ny1-(4)-2-isopropylthio-ethy1(1)]-dithl0phosphate 160/0.030,0-diethy1-S-[2-isopropoxy-l,3 4-thiadiazol-5 (4H)-ony1(4)-2-isopropylthio-ethyl(1')]-dithiophosphate 160/0.03

1 Calculated: C, 46.39; H, 5.45; N, 7.21; P, 7.99; 8, 16.51. Found: C,46.40; H, 5.60; N, 7.00; P, 8.00; S, 16.70.

2 Calculated (percent): N, 6.85; P, 7.59; S, 15.96; 01, 8.67. Found(percent): N, 6.30; P, 7.70; S, 16.00; 01, 8.90.

3 Undistillable oil. Calculated (percent): N, 6.66; P, 7.38; 8, 22.87.Found (percent): N, 6.00; P, 7.90; S, 22.70.

EXAMPLE 26 (a) Insecticidal contact-poison action (a In order to testthe active substances on polyvalent-resistant house flies (Muscadomestica), on mosquitoes (Aedes aegypti) and on stable flies (Stomoxyscalcitrans), coatings of the active substance were applied, usingacetonic solutions of the active substance, in Petri dishes, whereby thefollowing concentrations were used:

(a) 10 mg. of active substance per dish (for Musca),

(b) 1 mg. of active substance per dish (for Aedes),

(c) 1 mg. of active substance per square metre (for Stomoxys).

Stable es toes 0,0-diethyl-S-[Zethoxy-l,3,4,-thiadlazol-5(4H)-on-4-yl-ethyl-(1)]-dithlophosphate 0,0-dimethy1-S-[2-methylthio-13,4-thiadiazol-5(4H)-on 4-yl-ethyl(l)l-dithiophosphate0,0-dimethyl-S-[2-methoxy-l,3,4-thiadiazol-5(4H)-on-4-yl-(2-chloroethyl)-(1)]-dithi0phosphate 0,0-diethyl-S-[2-methoxy-1,3,4-thiadlazol-6(4H)on-4-yl-(2-chloroethyl)-(1')]- dithiophosphate0,0-dimethyI-S-[Z-ethoxy-l,3,4-thiadiazol-5(4H)-on-4-yl-(2-chloroethyl)-(1')]- dlthlophosphate0,0-diethy1-S-[2-ethoxy-1,3,4-thiadiazol-5(4H)-on-4-yl-(2chloroethyl)-(1)]- dithiophosphate0,0-dimethy1-S-[2-methoxy-1,3,4-thiadiazol-5(4H)-on-4-y1-(2-bromoethyl)-(1)]-dithiophosphnte0,0dimethyl-S-[Z-methoxy-1,3,4-thiadiazol-5(4H)-on4-yl-(2-methoxy-ethyl)(1)]-dithioph0sphate O, O-diethy1-S-[2-methoxy-1,3,4-thiadiazol-5(4H)-on-4-y1-(2-rnethylthloethyl)- (1)]-dithiophosphate0,0-d1methyl-S-[2-methoxy ,4-thladiazol-5(4H)bnt-yl-(2'-ethylthioethyl)-(1)]-dithiophosphate0,0-dimethyl-S-[2-meth0xy-1,3,4-thiadiazol-E(4H)-on-4-yl-(2'-is0propylthi0ethyl)-(1)]-dithiophosphate 0,0-dimethyl-S-[1 3,4-oxadiazl-5(4H)-on-4-y1-ethyl-(1) -dithiophosphate0,0-diethyl-S-[1,3,4-oxadiazo1-5(4H)-on- 4-yl-ethyl-(l)]-dithiophosphate0,0-dimethyl-S-[Z-methyl-l,3,4-oxndiazol-6(4H)-on-4-yl-ethy1-(1')]-dithiophosphate"; 0,O-diethyl-S-[2-methyl-l,3,4-oxadiazol-(4H)-on-4-y1-ethyl-(1)]-dithiophosphate 0,0-dimethy1-S-[L34-oxadiazol-5(4H)- on-l-yl-propyl-(l) -dithiophosphate.. 600,0.dimethyl-S-l2-methy1-1,3,4-oxadiazol-5 (4H)-on-4-yl-propyl-(1)]dithiophosphate O 0-dlethyl-S-[2-methyl-l,3,4-oxadiazo1- 5(4H)-on-4yl-propyl-(1)]-dithlophosphate 0,0-diethyl-S-[Z-methyl-l,3,4-oxadiazol-5(4H)-on-4-yl-lsobutyl(1)]-dithiophosphate (a An amount of mg. of a 1%dust was evenly distributed in Petri dishes; cockroaches (Phyllodromiagermanica and Perz'planeta americana) were then placed in the dishes andkept there under normal conditions at 22-24.

In the following table are given the times after which all insects werelying on their backs.

Minutes] hours (a Grain weevils were sprayed with 2 ml. of a 1% acetonicsolution of active substance from a distance of 10 cm. with a sprayer.Immediately after the application, the insects were transferred to cleanPetri dishes and kept there at 22. In the following table are given thetimes after which all'the insects were lying on their backs.

Minutes] hours0,0-dimethyl-S-[2-rnethylthio-l,3,4-thladiazol-5(4H)-on-4-y1-ethyl-(1)]-dithiophosphate 80,0dimethy1-S-[2-Inethoxy-1,3,4-thiadiazol-5-(4H)-on-4-yl-(2-chlorethyl)-(1)]-dithiophosphate 30,0-diethyl-S-[2-methoxy-l,3,4-thiadiaz01-5(4H)-on-4-yl-(2-chloroethyl)-(1)]-dithiophosphate 24 0,0-dimothyl-S-[Q-ethoxy-l,3,4'thiadiazol-5 (4H)-on-4-yl-(2- chloroethyl)-(1l]-dithiophosphate 80,0-diethyl-S-[2-ethoxy-1,3,4-thiadiazol-5(4H)-on-4-yl-(2-cholorethyl)-(1)]-dithiophosphate 80,0-dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5(4H)-on-4-yl-(2-methoxy-ethyl)-(l)]-dithiophospahte 150 0,O-diethyl-S-[2-methoxy-1,8,4-thiadiazol-5(4H)-on-4-yl-(2-methylthio-ethyl)-(l')]-dithiophosphate 5 0,0-dimethyl-S-[l,3,4-oxadiazol-5(4H) -on-4-y1-ethyl-(1')]- dithiophosphate. 420,0-diethyl-S-[1,3,4-oxadiazol-5(4H)-on-4-yl-et;hyl-(1)]-dithiophosphate 70' O O-dimethyl-S-[2-methy1-1,3,4-oxadiazol-5(4H)-on-4-yl-ethyl- (1)]-dithiophosphate 6 0O-diethyl-S-[2-methy14,3,4-oxadiazol-5(4H) -0n-4-yl-ethyl-(1')]-dithi0phosphate 24 0 Odimethyl-S-[I,3,4-oxadiazol-5 (4H)-on-4-yl-propyl- (1')]- dithiophosphate. 0,O-diethyl-S-[2-methyl-1,3,4-oxadia201-5 (4H) -on-4-yl-propyl-(1)]-dithiophosphate 5 (b) Insecticidal lasting efiect (b-a) On glass:Petri dishes containing coatings of active substance of 1 g. of activesubstance per square metre were allowed to stand for 7 days at 24.Polyvalent houseflies, mosquitoes and stable flies were then placed ontothe coatings.

(b-b) On wood: The active substances were applied from aqueoussuspension to wooden boards, the concentration being 1 g. of activesubstance per square metre. The above stated test insects were placedafter 8 days onto the treated boards.

In the following table is given the time in hours and minutes afterwhich the insects were in the on-the-back position.

Stable flies House Mosquies toes (c) Systemic-insecticidal action Inorder to determine the systemic action, the soil of potted bean plantswas watered per 600 cubic centimetres with 50 ml. of an aqueous emulsioncontaining 100 ppm. of active substance (emulsion obtained from a 10%emulsifiable concentrate).

After 3 days, aphis (aphis fabae) were placed onto the parts of theplants above the soil. The insects were protected by a special devicefrom the contact and gas What is claimed is: 1. Compounds of theformula:

wherein R represents lower alkyl, lower alkoxy or phenyl,

R represents lower alkyl,

R represents lower alkyl, chloro lower alkyl, bromo lower alkyl, loweralkoxyalkyl, lower alkylthioalkyl, phenyl,

R represents hydrogen, lower alkyl, lower alkoxy, lower alkylthio,phenyl,

and the symbols X, Y and Z represent, independently of each other,oxygen or sulphur.

2. Compounds according to claim 1 of the formula:

wherein R and R each represent methyl or ethyl; R

represents methyl, ethyl, C3H7(i), chloromethyl, bromomethyl, -'CHZOCH3,CH2SCH3, -'CH2SCzH5, --C-H SC H-;(i), or phenyl;

R represents hydrogen, methyl, methoxy, ethoxy, isopropoxy, methylthio,or phenyl; and X, Y and Z each represent oxygen or sulphur.

3. Compound according to claim 2 of the formula:

CHaO\ /S S P o=o S--(IJHI I CH:

4. Compound according to claim 2 of the formula:

C|H5O\ %S /S\ P =o o-oom \S-OH-I!IN C-O CH:

CHsO

5. Compound according to claim 2 of the formula:

6. Compound according to claim 2 of the formula:

7. Compound according to claim 2 of the formula:

C-S CH:

CH: O

8. Compound according to claim 2 of the formula:

9. Compound according to claim 2 of the formula:

l CHsO CH:

10. Compound according to claim 2 of the formula:

11. Compound according to claim 2 of the formula:

12. Compound according to claim 2 of the formula:

13. Compound according to claim 2 of the formula:

14. Compound according to claim 2 of the formula:

15. Compound according to claim 2 of the formula:

16. Compound according to claim 2 of the formula:

17. Compound according to claim 2 of the formula:

24 18. Compound according to claim 2 of the formula: 29. Compoundaccording to claim 2 of the formula:

CzHsO\ S /o\ CH:\ s /s /P 0:0 (ll-CH; /P 0:? (17-0 CZHS OM 0 SCHNN 5011,0 S(|JIINN $311 0 011,13: Compound according to claim 2 of theformula: 30. Compound according to claim 2 of the formula:

cm0 s s\ C2H5O\ 0:0 $001k 10 1* o=c o-o 01m CHSO S CH N N omtoSCHI!I-ILI mm mm 20. Compound according to claim 2 of the formula:

0,1150 8 s 31. Compound according to claim 2 of the formula:

\fi cH o\ s s 021140 SCHN- N P 0= |3 ("J-S om H201 CHSO S-OH-N-N H11321. Compound according to claim 2 of the formula:

CHSO S S 32. Compound according to claim 2 of the formula:

P O=('J/ \fi 0 2H5 C2H50\ S /S\ 01110 SCHN-N 0-8 H201 0111 0 SCH-N-N 0mm22. Compound according to claim 2 of the formula:

CIHSO S s 33. Compound according to claim 2 of the formula:

P 0=cl: 30 01H CHIC)\ 0,1150 SCHNN C OCH H2 01 crno SCHN-N H SCHa 23. Coound accordin to claim 2 of the formula:

mp g 34. Compound according to claim 2 of the formula:

24. Compound according to claim 2 of the formula:

CzH5O s s 35. Compound according to claim 2 of the formula:

P O=C C-O CsH1(l) 0211.0 SCH-NN fi Cam H101 cmo S--OHNN 25. Compoundaccording to claim 2. of the formula: Hzs CH2 36. Compound according toclaim 2 of the formula:

P\ 0:? o-s CH3 omo SCHNN ozH6O\ P o=0 0-0 0,11, H201 H I I 021150 26.Compound accordlng to claim 2 of the formula: HISCH CZHSO s s I fi 37.Compound according to claim 2 of the formula.

s s C:H5O s CH N N CH30\ H201 /P\ 0:? f-o 0H, 27. Compound according toclaim 2 of the formula: Snell-N N CHO\ s S H1O CH3 1 0=o c-ocmReferences Cited cmo S-CHI I-N UNITED STATES PATENTS CHzBr 2,706,194 4/1955 Morris et al 260-302 E 3,239,532 3/1966 Ruf ht 260---302 E 28.Compound according to claim 2 of the formula: enac CzH5O\ s s RICHARD J.GALLAGHER, Primary Examiner US. Cl. X.R. CzHso \SC'HII\II 260-302 D, 307A; 424-200 CHzBl UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONPatent No. 3 766 200 Dated October 16 1973 ll Invent0r( Kurt RufenaohtIt is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

"The following should be inserted in the heading:

Claims priority, application Switzerland July 2, 1970 No. 10042/70Signed and sealed this 16th day of July 1971p.

(SEAL) Attest:

MCCOY M. GIBSON, JR. C. MARSHALL DANN Commissioner of Patents AttestingOfficer FORM PO-1050 (10-69) UscoMM Dc 6376 P69 u.s. covznuuzu'rPRINTING orncs 1909 o-sas-san,

